BR112017009827B1 - ADSORPTION COMPLEX COMPRISING 1-MCP (1-METHYLCYCLOPROPENE) AND A METAL COORDINATION POLYMER NET, KIT TO CONTAIN 1-MCP AND METHOD TO RELEASE 1-MCP FROM AN ADSORPTION COMPLEX FORMULATION KIT - Google Patents

Abstract

abstract ?1-methylcyclopropene complexes with metal coordination polymer networks? Adsorption complexes are disclosed that include 1-methylcyclopropene (1-mcp) and a metal coordination polymer (mcpn) network, wherein the mcpn is a porous material, and the 1-mcp is adsorbed onto the mcpn. kits are also disclosed to contain 1-mcp which include the adsorption complex in a waterproof package of 1-mcp. also disclosed are methods of releasing 1-methylcyclopropene (1-mcp) from the kit which include the application of aqueous fluids, heat and/or pressure.

Description

Cross Reference to Related Orders

[001] This application claims priority to US Patent Application No. 14/726,004, filed May 29, 2015, which claims priority to US Provisional Patent Application No. 62/077,867, filed November 10, 2014, titled “Forming Complexes of Cyclopropenes with Metallic Coordination Polymer Network for Plant and Plant Parts Application” each of which is hereby incorporated by reference in its entirety.

Technical Field

[002] Embodiments refer to methods and compositions for the adsorption, storage and handling of volatile cyclopropene compounds, such as 1-methylcyclopropene.

Government Support Recognition

[003] This invention was made with government support under Grant Number 2014-33610-21957 granted by the National Institute of Food and Agriculture, United States Department of Agriculture. The government has certain rights in the invention.

Fundamentals

[004] Cyclopropene compounds are widely used to advantageously control the effects of ethylene on plants to delay ripening and senescence, for example, to extend the shelf life of harvested products. Due to the inherent volatility of cyclopropene compounds and their potential to undergo oxidation, these compounds cannot be stored in a gaseous state for long periods of time. Additionally, some cyclopropenes, such as 1-methylcyclopropene gas (1-MCP), are flammable and present an explosion hazard when compressed. The difficulty of storing and handling 1-MCP limits its usefulness.

Brief Description of Drawings

[005] Embodiments will be readily understood by the following detailed description in conjunction with the accompanying drawings. Embodiments are illustrated by way of example and not by way of limitation in the figures of the accompanying drawings.

[006] Figures 1A-D illustrate chromatograms of 1-MCP released by solid (Figures 1B and 1C) and solution (Figures 1A and 1D) methods for MCPN adsorption complexes (Figures 1B and 1D) and molecular encapsulation complexes of α-cyclodextrin (Figures 1A and 1C), and show data corresponding to Table 2, according to various embodiments;

[007] Figure 2 is a bar graph illustrating levels of inclusion of 1-MCP in various MCPNs (S1, S2 and S3) using a solid adsorption method, and shows data that correspond to Table 3, according to various embodiments;

[008] Figure 3 is a graph illustrating the release of 1-MCP by suspending the encapsulating and absorbent complexes in water of S1 (method A) and S4 (method D), and shows data corresponding to Table 4 of according to various embodiments;

[009] Figure 4 is a graph illustrating the release of 1-MCP from the encapsulating and absorbent complexes by heating to 50 °C, and shows data corresponding to Table 5, according to various embodiments;

[0010] Figures 5A and 5B are two digital images showing TEM analyzes of MCPN before and after complex formation with 1-MCP; according to various embodiments; and

[0011] Figures 6A and 6B illustrate the X-ray diffraction patterns of MCPN before (Figure 6A) and after (Figure 6B) dissolution in water, according to various embodiments.

Detailed Description of Disclosed Forms of Achievement

[0012] In the following detailed description, reference will be made to the accompanying drawings which form a part thereof, and which are shown by way of illustrative embodiments which can be practiced. It should be understood that other embodiments can be used and structural or logical changes can be made without departing from scope. Therefore, the following detailed description is not to be taken in a limiting sense, and the scope of embodiments is defined by the appended claims and their equivalents.

[0013] Several operations can be described as multiple distinct operations in turn, in a way that can be useful to understand embodiments; however, the order of description should not be interpreted to imply that these operations are order-dependent.

[0014]The description may use perspective-based descriptions such as high/low, back/front and top/bottom. Such descriptions are merely used to facilitate discussion and are not intended to restrict the application of the disclosed embodiments.

Terms

[0015] The terms "coupled" and "connected", together with their derivatives, may be used. It should be understood that these terms are not intended to be synonymous with each other. Instead, in particular embodiments, "connected" can be used to indicate that two or more elements are in direct physical or electrical contact with each other. “Coupled” can mean that two or more elements are in direct physical or electrical contact. However, “coupled” can also mean that two or more elements are not in direct contact with each other, but still cooperate or interact with each other.

[0016]For the purposes of description, a phrase in the form "A/B" or in the form "A and/or B" means (A), (B) or (A and B). For the purposes of description, a phrase of the form "at least one of A, B and C" means (A), (B), (C), (A and B), (A and C), (B and C ) or (A, B and C). For the purposes of description, a phrase of the form “(A)B” means (B) or (AB) that is, A is an optional element.

[0017] The description may use the terms "embodiment" or "embodiments", which may each refer to one or more of the same or different embodiments. In addition, the terms "comprising", "including", "having", and the like, as used with respect to the embodiments, are synonymous.

[0018] As used here, ranges are used as a shorthand to describe each and every value that is within the range. Any value within range can be selected as the end of the range.

[0019] Unless otherwise specified, all percentages and quantities expressed herein and elsewhere in the specification are to be understood as referring to percentages by weight. The quantities given are based on the active weight of the material.

[0020]Unless otherwise noted, technical terms are used in accordance with conventional usage. Furthermore, unless otherwise explained, all technical and scientific terms used herein have the same meaning as commonly understood by a person of ordinary skill in the art to which this disclosure belongs. The singular terms "a" and "the" include plural referents unless the context clearly indicates otherwise. Similarly, the word "or" is intended to include "and" unless the context clearly indicates otherwise. It is further to be understood that all base sizes or amino acid sizes, and all molecular weight or molecular weight values, given for nucleic acids or polypeptides are approximate, and are provided for description. While methods and materials similar or equivalent to those described herein can be used in the practice or testing of this disclosure, suitable methods and materials are described below. The term "comprises" means "includes". The abbreviation, “e.g.”, is derived from the Latin exempli gratia, and is used here to indicate a non-limiting example. Thus, the abbreviation “e.g.” is synonymous with the term “for example”.

[0021]Adsorption: Adhesion of atoms, ions or molecules from a gas, liquid or solid dissolved to a surface. Adsorption is a process other than absorption whereby in absorption molecules are taken up in the mass of another matter, not the surface of another matter (as with adsorption). A more general term is sorption, which covers adsorption, absorption and ion exchange. Adsorption is distinguished from molecular encapsulation, which is a specific binding process by which a substrate selectively adapts to an encapsulation site. Molecular encapsulation specificity can include stereochemical adaptation, electrostatic complementarity and a complementary arrangement of hydrophobic and hydrogen bond interactions.

[0022]Adsorption complex: A complex of a cyclopropene compound and a metal coordination polymer network (MCPN). For example, an adsorption complex can include 1-methylcyclopropene (1-MCP) and a metal coordination polymer network (MCPN).

[0023]Cyclopropene: An organic compound with the formula C3H4. It is the simplest cycloalkene. It has a triangular structure. Cyclopropene compounds/derivatives are disclosed, such as 1-methylcyclopropene (1-MCP; molecular formula C4H6), or other cyclopropene derivatives (Boryrenes, phosphirenes, and silyrenes are boron-, phosphorus- and silicon-substituted cyclopropenes, with the formula RBC2R'2, RPC2R'2 and R2SiC2R'2, respectively) which can be adsorbed by an MCPN to form an adsorption complex.

[0024]Ethylene (C2H4): A gaseous plant hormone that affects a myriad of developmental processes and fitness responses in plants, such as germination, flower and leaf senescence, fruit maturation, leaf abscission, root nodulation, death programmed cell and responsiveness to stress and pathogen attack.

[0025]Inhibition: To decrease, limit or block the action or function of a molecule. In one example, an ethylene-mediated response, such as ethylene binding to a plant ethylene receptor, is diminished, limited or blocked by a disclosed adsorption complex. For example, a disclosed adsorption complex inhibits or reduces the binding of ethylene to the ethylene receptor by at least 10%, at least 20%, at least 50%, or even at least 90%, including between about 10% to about 95%, about 20% to about 80%, about 30% to about 70%, about 40% to about 50%, such as 10%, 20%, 30%, 40%, 50% , 60%, 70%, 80%, 85%, 90%, 95%, 98% or 100%. Such decreases can be measured using the methods disclosed herein. In particular, a disclosed adsorption complex is used to inhibit, reduce or delay fruit ripening. For example, a disclosed adsorption complex can delay or inhibit the internal concentration of naturally produced ethylene increasing to about 0.1 to 1.0 (ppm).

[0026] Metal Coordination Polymeric Network (MCPN) Composition: A porous metal-containing composition that is capable of adsorbing 1-MCP. An MCPN can include a metal knot, such as Mg, Mn, Ca, Cu, Al, Zn, Fe, or Co, that is coupled to one or more linkers, such as an amino acid or a food additive, such as citric acid.

[0027]Permeance or permeation: The degree to which a material admits a flow of matter or transmits another substance. Permeable materials are those through which gases or liquids can pass. Permeable materials exhibit different permeances, eg permeation rates for different chemical species. In this regard, permeselectivity is the preferred permeation of a chemical species through a material with respect to another chemical species. Permeselectivity of the desired permeate with respect to another chemical species is calculated as the ratio of the permeate of the desired permeate to the permeation of the other chemical species.

[0028]Plant: A term referring to an entire plant, a part of the plant, a plant cell or a group of plant cells, such as plant tissue, for example.

[0029] Pore: One of the many openings or voids in a solid substance of any kind that contribute to the substance's porosity.

[0030]Porosity is a measure of the voids or openings in a material, and is measured as a fraction, between 0 to 1, or as a percentage between 0 to 100%.

[0031]Porous: A term used to describe a matrix or material that is permeable to fluids. For example, a porous matrix or material is a matrix/material that is permeated by an interconnected network of pores (voids) that can be filled with a fluid (such as a liquid or gas). In some examples, the matrix and pore lattice (also known as the pore space) is continuous, as well as to form two interpenetrating continuums.

Description of Various Forms of Achievement

[0032] Embodiments herein provide polymeric metal coordination networks (MCPNs) that can be used to adsorb materials such as cyclopropene compounds/derivatives into the pores in their structures. Cyclopropene compounds can be used to extend the shelf life of plant products such as agricultural produce, cut flowers, and the like. For example, US Patent No. 5,518,988 describes various methods of using cyclopropene compounds to inhibit ethylene responses in plants.

[0033] A particularly effective cyclopropene for blocking ethylene receptors in plants is 1-methylcyclopropene (1-MCP), which is a volatile gas. The volatility of 1-MCP presents special challenges as the compound cannot be stored in a gaseous state for long periods of time. Additionally, 1-MCP gas is flammable and presents an explosion hazard when compressed. The inherent difficulties in storing and handling 1-MCP limit the ways in which it can be used to inhibit ethylene responses in plants.

[0034]Several strategies were used in storing, handling and applying 1-MCP. For example, US Patent 6,017,849 discloses a method of forming complexes between 1-MCP and encapsulating molecular agents such as cyclodextrin, thereby providing a convenient means of storing and transporting these compounds. Cyclodextrins are cyclic oligosaccharides made up of six or more α-D-glucopyranose units that are linked through (α-1,4)-glycosidic bonds. The chair conformations of the individual glucose unit in the ring give the cyclodextrins their conical toroidal shape, with the primary hydroxyl functions of the individual sugar molecules extending from the narrow end of the torus, and the secondary hydroxyl groups extending from the end. wider away from the inner cavity in the outer cone. The internal cavity of the cyclodextrin torus is composed of the skeletal carbons and the ether bond of the α-1,4 linked D-glucopyranose units giving the internal cavity of the cyclodextrin its lipophilic character.

[0035] A complex between 1-MCP and a cyclodextrin is formed when a single 1-MCP molecule enters the internal cavity of the cyclodextrin torus to form a complex that has been compared to a "lock and key structure" that is similar to an enzyme by which a substrate selectively adapts to the encapsulation site. Of the available cyclodextrins, α-cyclodextrin has been commercially exploited as a molecular encapsulation agent for 1-MCP, but stable complex formation of 1-MCP and β- and Y—cyclodextrins has not been achieved. Encapsulation of a smaller molecule such as 1-MCP in β- or Y-cyclodextrin is a challenge due to the larger internal cavities of β- and Y-cyclodextrins, which weaken the resulting complex due to an insufficiently tight “lock and key” interaction between the molecules. As α-cyclodextrin is considerably more expensive than β- and Y-cyclodextrins, molecular encapsulation of 1-MCP with α-cyclodextrin can be expensive.

[0036] In contrast, the MCPNs disclosed here are a cheaper option to isolate 1-MCP for safe use and handling, and more options are available since a size-based “lock and key” type filling is not required with an adsorption-based complexation process. Generally speaking, MCPNs for use in the various embodiments disclosed herein include any porous MCPN composition that is capable of adsorbing 1-MCP. In various embodiments, the MCPN can include a metal knot that is coupled to one or more binders. For example, in various embodiments, the metal knot can be Mg, Mn, Ca, Cu, Al, Zn, Fe or Co. In some embodiments, the binder can be an amino acid or a food additive such as Citric acid. In some embodiments, an MCPN is any porous MCPN composition capable of adsorbing 1-MCP, but does not include cyclodextrin or derivatives thereof. In some embodiments, an MCPN is any porous MCPN composition capable of adsorbing 1-MCP, but does not form a lock and key structure with 1-MCP.

[0037] In some embodiments, the MCPN may be a calcium coordination polymer network. A specific non-limiting example of a calcium coordination polymer network that can be used is [Ca(4,4'-sulfonyldibenzoate)].H2O. Other specific non-limiting examples of MCPNs for use in various embodiments include Cu-TDPAT, also referred to as 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine, Zn2(tcbpe), also referred to as the reaction product of tetra-(4-bromo-phenyl)ethylene (tpe-Br) and 4-(methoxycarbonyl)phenylboronic acid, [Co3(biphenyldicarboxylate)34,4'bipyridine].4DMF.H2O, [Co (biphenyldicarboxylate)(4,4'bipyridine)].0.5DMF, [Zn2(biphenyldicarboxylate)2(1,2-bipyridylethylene)].2DMF, Mg3(O2C-C10-H6-CO2)3, magnesium formate, terephthalate of aluminum, Cu3(benzene-1,3,5-tricarboxylate)2, Fe(1,3,5-benzenetricarboxylate), 2-methylimidazole zinc salt, Co(2-methylimidazole)2 and Al(OH)fumarate.

[0038]The MCPNs listed above are solids synthesized in a solvent (such as DMF and water). In various embodiments, after the network is formed, the solvent can be removed by heating. For example, in various embodiments, MCPN materials can be heat activated to remove all moisture or solvents prior to use.

[0039] Adsorption of 1-MCP by MCPNs can be performed in a variety of ways, including both solid-based and solution-based methods, as disclosed herein in various embodiments. In various embodiments, the general protocol in both methods may include a dual-vessel system, wherein 1-MCP is generated in the first vessel, also referred to as the generation vessel, and adsorption occurs in the second vessel, also referred to. as the adsorption vessel. In some examples, prior to adsorption, the adsorbent may first be dried in a vacuum oven and sealed in the adsorption vessel. 1-MCP can be generated in the generation vessel and introduced to the adsorption vessel for adsorption by the MCPN. In various embodiments, adsorption can be carried out with continuous agitation of the adsorbent.

[0040] In various embodiments, since 1-MCP has been adsorbed by MCPN, MCPN-1-MCP complexes can be formed into tablets or other unitary formulations for ease of use. For example, in some embodiments, MCPN-containing tablets can be manufactured using starch or starch-like materials, while in other embodiments they can also include food grade starch such as corn starch or other modified starches (eg, dextrin , acetylated starch, alkaline modified starch, methylated carboxy starch, and acetylated oxidized starch). In some embodiments, the starches can be fast and easy gelling starches having water-based materials, or they can be slow gelling. In some embodiments, tablets or other unitary formulations may include other filler materials, such as inert materials, such as clay, which have the ability to slowly swell or disintegrate with the addition of water-based material (eg, kaolin clay. ). Other fillers can include gums such as xanthan gum (CP Kelko, Atlanta, GA), carboxy methyl cellulose (CP Kelko, Atlanta, GA), caragenane (CP Kelko, Atlanta, GA), hydroxyl propyl cellulose (CP Kelko, Atlanta, GA ) and hydroxyl ethyl cellulose (CP Kelko, Atlanta, GA).

[0041] In various embodiments, tablets can be coated. Specific non-limiting examples of coating materials include polymethacrylates, cellulose-based polymers (eg, cellulose acetate phthalate or hydroxypropylmethylcellulose phthalate), polyvinyl derivatives (eg, polyvinyl acetate phthalate), and other copolymers (eg, hemi-esters of styrene maleic acid copolymersate). In various embodiments, other ingredients in the coating material can include plasticizers, anti-adhesive agents, colorants or pigments, solubilizers or dispersing agents, and other additives.

[0042] In some embodiments, MCPN-1-MCP complexes can be contained within capsules. Specific non-limiting examples of capsules for use in accordance with various embodiments include gelatin capsules and hydroxylpropyl methylcellulose capsules (Capsugel, Morristown, NJ). In various embodiments, suitable capsules can also include any material which has low gas permeability properties but which can permeate water vapor, such as nylon or PVOH based capsules, or any other starch or gum based capsules. (eg, carboxymethylcellulose).

[0043] In some embodiments, coatings for capsules can also be used. For example, in specific non-limiting examples, coating materials can include polymethacrylates, cellulose-based polymers (eg, cellulose acetate phthalate and hydroxypropylmethylcellulose phthalate), polyvinyl derivatives (eg, polyvinyl acetate phthalate), and other copolymers (eg, hemi-esters of copolymerized styrene and maleic acid). Other ingredients in coating materials can include plasticizers, anti-adhesive agents, colorants or pigments, solubilizers or dispersing agents, and other additives.

[0044] In various embodiments, capsules may include fillers within the capsules, hereinafter referred to as capsule fillers, which may include 100% non-aqueous material, or non-aqueous material containing less than 2% material aqueous, which disperses the MCPN-1-MCP complex, minimizes the loss of 1-MCP, and achieves at least 90% retention of active ingredient in the formulation when heat, pressure, or aqueous-based solution such as water is not used. is used to release the active ingredient. Specific non-limiting examples of non-aqueous (or less than 2% aqueous) materials include hydrophobic/non-aqueous liquids such as mineral oil or other vegetable-based oils, polyols, (eg, glycerol, 99.9% pure , 0.1% water, Sigma Aldrich Co., St. Louis, MO) and D-sorbitol (98% pure, Sigma Aldrich Co., St. Louis, MO). Other polyols that can be used include di-, tri- and tetrols and other sugar alcohols and/or mixtures thereof. Other specific non-limiting examples of capsule fillers include gums that have the ability to hydrate with the addition of aqueous solution or water vapor, such as xanthan gum (CP Kelko, Atlanta, GA), carboxy methyl cellulose (CP Kelko, Atlanta, GA ), caragenan (CP Kelko, Atlanta, GA), hydroxyl propyl cellulose (CP Kelko, Atlanta, GA) and hydroxyl ethyl cellulose (CP Kelko, Atlanta, GA). Other specific non-limiting examples of capsule fillers include starches (e.g., food grade starch such as corn starch) or other modified starches (e.g., dextrin, acetylated starch, alkaline modified starch, methylated carboxy starch and acetylated oxidized starch). In various embodiments, capsule fillers can also be used directly for application to plant or vegetable-based material as a liquid formulation for drainage or spraying.

[0045] In various embodiments, MCPNs that are for capsule fillers or liquid formulations can have a particle size with a lower limit of at least 0.05mm, such as 0.10mm or higher. In various embodiments, such MCPNs can have an upper size limit of 5mm or lower, such as 3mm or lower or 1.5mm or lower.

[0046] Various methods can be used to release 1-MCP from the MCPN-1-MCP complex, for example, to treat plants or plant parts to inhibit an ethylene response. In some embodiments, the MCPN-1-MCP complex can be contacted with water, which can open the MCPN structure. In various embodiments, this can cause 1-MCP to be released as a gas, which can then be applied or directed to desired plant materials in a closed environment.

[0047] In other embodiments, heat or pressure can be used to release 1-MCP from the MCPN-1-MCP complex in order to inhibit an ethylene response in a plant or plant parts. In various embodiments, the release temperature of 1-MCP can be about 35°C or higher, such as 50°C or higher. In various embodiments, the upper limit for releasing 1-MCP from the MCPN-1-MCP complex can be about 100°C or lower, such as 80°C or lower or 60°C or lower . In various embodiments, although temperatures higher than these cut-off values can be used to release 1-MCP from the MCPN-1-MCP complex (MCPNs are generally thermostable to about 575 °C) in some embodiments, significant degradation of 1-MCP can occur above 60°C, which can affect the biological activity of 1-MCP. In embodiments where pressure is used to release 1-MCP from the MCPN-1-MCP complex, the release pressure is generally about 5 millibars or higher, such as 10 millibars or higher or 15 millibars or higher. In various embodiments, the upper limit for release pressure can be an internal pack pressure of 400 millibars or lower, such as 300 millibars or lower, 200 millibars or lower, or 100 millibars or lower. Although exemplary temperature and pressure ranges are provided, a person of skill in the art will appreciate that other techniques or modifications may be used to aid in the release of 1-MCP from the MCPN-1-MCP complex.

[0048] In various embodiments, MCPN-1-MCP complex sachets can be used, for example, in certain box, pallet, cooler container or storage room applications. In various embodiments, the inherent 1-MCP and moisture transmission characteristics of the polymeric film (or portion thereof) forming the outside of the sachets can be characterized, such as the properties of the film itself, in the absence of any perforations or other changes that can be included to help with 1-MCP release. For example, in some embodiments, the composition of a film can be characterized by characterizing the moisture transmission characteristics of the film using a standard film thickness, such as a film having a thickness of about 25.4 micrometers. For films having different thicknesses than the standard thickness (eg, from 8 to 76.2 micrometers), a person skilled in the art can easily and accurately calculate the equivalent moisture transmission characteristics of a film having the same composition, but having a standard thickness of 25.4 micrometers or 1 mil, for example, to compare moisture transmission characteristics of two films having different thicknesses. In various embodiments, the 1-MCP or moisture transmission rate of a film having a thickness of 25.4 micrometers is labeled "FL-1" here.

Specific non-limiting examples of film compositions for use in various embodiments are where the FL-1 for 1-MCP transmission at 23°C, in units of cm 3 /(m 2 -day), is 800 or taller; such as 4,000 or higher, 5,000 or higher, 10,000 or higher, or 20,000 or higher. Other specific non-limiting examples of film compositions for use in various embodiments include films with FL-1 for transmitting 1-MCP at 23°C, in units of cm 3 /(m 2 -day), may be 150,000 or lower , such as 80,000 or lower or 60,000 or lower. In specific non-limiting examples, films for use in various embodiments may be films with FL-1 for water vapor at 37.8°C, in units of g/(m 2 -day), such as 5 or higher, or 25 or higher. In other specific non-limiting examples, films for use in various embodiments may be films with FL-1 for water vapor at 37.8°C, in units of g/(m 2 -day), of 350 or lower, such as 200 or lower, or 100 or lower.

[0050] In various embodiments, some or all of the inner and outer surface of the sachets can be polymeric. In various embodiments, the polymer can be a polymeric film or coating. In some embodiments, polymeric film or coating layers for use in various embodiments may have an average thickness of 1 micrometer or more, such as 5 micrometer or more, or 10 micrometer or more. In some embodiments, polymeric film or coating layers for use in various embodiments may have an average thickness of 250 micrometers or less, such as 200 micrometers or less, 100 micrometers or less, or 75 micrometers or less.

[0051] In some embodiments, the amount of adsorbed 1-MCP present in the overall composition of the MCPN-1-MCP complex may be 0.001% by weight of active ingredient (ai) or more, such as 0.005% by weight of ai or more, or 0.05% by weight of ai or more. In some embodiments, the amount of adsorbed 1-MCP present in the overall composition of the MCPN-1-MCP complex may be 25% by weight ai or less, such as 20% by weight ai or less, or 15% by weight of ai or less.

[0052] In some embodiments, the MCPN may have a total porosity of 0.001% by volume or more, such as 0.005% by volume or more, or 0.05% by volume or more. In some embodiments, the MCPN can have a total porosity of 50% by volume or less, such as 40% by volume or less, or 25% by volume or less.

[0053] In some embodiments, the MCPN may have the ability to break the coordination network on water.

Examples Example 1: Synthesis of 1-MCP

[0054] This example describes an exemplary method for the synthesis of 1-MCP. 1-MCP was generated from a 1-MCP-Li suspension in mineral oil, which was prepared by reacting lithium diisopropylamide (LDA) with 3-chloro-2-methylpropene under a nitrogen environment which is described in "Kinetics of Molecular Encapsulation of 1-Methylcyclopropene into α-Cyclodextrin", Journal of Agricultural and Food Chemistry, 55(26): pages 11020 - 11026, which is incorporated herein by reference. Table 1 summarizes the reaction conditions used to synthesize 1-MCP. Table 1: Reaction conditions for synthesizing 1-MCP

Example 2: MCPNs and their Synthesis

[0055]This Example provides specific examples of MCPNs for use in various embodiments and methods of their synthesis. In some embodiments, the MCPN can be a calcium coordination polymer network. A specific non-limiting example of a calcium coordination polymer network that can be used is [Ca(4,4'-sulfonyldibenzoate)].H2O. The synthesis and structural properties of [Ca(4,4'-sulfonyldibenzoate)].H2O are described in “A Calcium Coordination Framework Having Permanent Porosity and High CO2/N2 Selectivity”, Banerjee et al., Cristal Growth and Design, 2012, 2162 - 2165, which is incorporated herein by reference in its entirety. Briefly, in a specific example, [Ca(4,4'-sulfonyldibenzoate)]. H2O was synthesized according to the following protocol: a mixture of 0.0006 mol of CaCl2 (0.074g) and 0.0006 mol of 4.4'-SDB (0.198 grams) was dissolved in 10.05 grams of ethanol and stirred for 2 hours to obtain homogeneity [molar ratio of metal chloride:binder:solvent = 1:1:380]. The resulting solution was heated at 180 °C for 5 days. Colorless needle-shaped crystals were recovered as products and washed with ethanol (Yield: 50% based on calcium in anhydrous CaCl 2 , 0.112 gram). The water in the final product was derived from 95% ethanol solvent and moisture adsorbed onto the CaCl2 reagent.

In other embodiments, the MCPN can be Cu-TDPAT, also referred to as 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine. The synthesis and structural properties of Cu-TDPAT are described in "Stability and Hydrogen Adsorption of Metal Organic Frameworks Prepared via Different Catalyst Doping Methods", Wang et al., Journal of Catalysis, 2014. 318(0): pages 128 - 142, which is incorporated herein by reference in its entirety. In a specific non-limiting example, Cu-TDPAT crystals were cultured by a reaction of 0.68 mmol Cu(NO3)2'6H2O, 0.05 mmol H6TDPAT in 2 mL DMA (dimethylacetamide), 2 mL DMSO ( dimethyl sulfoxide), 0.2 mL of H2O and 0.9 mL of HBF4 at 358 K for three days. Blue polyhedron crystals ([Cu3(TDPAT)(H2θ)3]-10H2θ-5DMA) were collected and then washed with 10 mL of DMA three times. Methanol exchange was performed every 1 hour during the day for one week by solvent exchange.

[0057] In other embodiments, the MCPN can be Zn2(tcbpe), also referred to as the reaction product of tetra-(4-bromo-phenyl)ethylene (tpe-Br) and 4-(methoxycarbonyl)phenylboronic acid. A typical synthesis of Zn2(tcbpe) is as follows: Zn(NO3)2'6H2O (0.0892 gram, 0.30 mmol), H4tcbpe (0.0244 gram, 0.03 mmol), and N,N' -dimethylacetamide (DMA, 2 mL) are loaded into a 20 mL glass vial. The glass vial is capped and sonicated at room temperature for a few minutes until a clear solution is obtained. The sealed glass vial is then placed at 120 °C for a 48 hour reaction. Clear light yellow single crystals are collected by filtration, washed with DMA and air dried.

[0058] In other embodiments, the MCPN can be [Co3(biphenyldicarboxylate)34,4'bipyridine].4DMF.H2O. The synthesis and properties of [Co3(biphenyldicarboxylate)34,4'bipyridine].4DMF.H2O are described in "A Recyclable Nanoporous Material Suitable for Ship-In-Bottle Synthesis and Large Hydrocarbon Sorption", Long Pan et al., Angew. Chem. Int. Ed. 2003, 42, No. 5, pages 542 - 546, which is incorporated herein by reference in its entirety. In this publication, [Co3(biphenyldicarboxylate)34,4'-bipyridine],4DMF.H2O is referred to as [Co3(bpdc)3bpy],4DMF.H2O, where bpdc is biphenyldicarboxylate and bpy is 4,4'-bipyridine, and DMF refers to N,N-dimethylformamide.

[0059] In another embodiment, the MCPN can be [Co(biphenyldicarboxylate)(4,4'bipyridine)].0.5DMF. The synthesis and properties of [Co(biphenyldicarboxylate)(4,4'bipyridine)].0.5DMF are described in "A Recyclable Porous Material with Unusual Adsorption Capability: Self Assembly via Structural Transformations", Long Pan et al., Chem. Commun., 2003, pages 854 - 855, which is incorporated herein by reference in its entirety. In this publication, [Co(biphenyldicarboxylate)(4,4'-bipyridine)].0.5DMF is referred to as [Co(bpdc)(bpy)].0.5DMF.

[0060] In another embodiment, the MCPN can be [Zn2(biphenyldicarboxylate)2(1,2-bipyridylethylene)].2DMF. The synthesis and properties of [Zn2(biphenyldicarboxylate)2(1,2-bipyridylethylene)].2DMF are described in "A Multifunctional Microporous MOF with Recyclable Framework and High H2 Binding Energy", Anjian Lan et al., Inorg. Chem. 2009, 48, pages 7165 - 7173, and in “A Luminescent Microporous Metal-Organic Framework for the Fast and Reversible Detection of High Explosives”, Anjian Lan, Angew. Chem. Int. Ed. 2009, 48, pages 2334 - 2338, both of which are incorporated herein by reference in their entirety. In this latter reference, [Zn2(biphenyldicarboxylate)2(1,2-bipyridylethylene)].2DMF is referred to as [Zn2(bpdc)2(bpee)].2DMF, where bpee is 1,2-bipyridylethylene.

[0061] In another embodiment, the MCPN can be Mg3(O2C-C10-H6-CO2)3. The synthesis and properties of Mg3(O2C-C10-H6-CO2)3 are described in "Strong H2 Binding and Selective Gas Adsorption within the Microporous Coordination Solid Mg3(O2C-C10-H6-CO2)3", Mircea Dinca et al. , J. Am. Chem. Soc., 2005, 127, pages 9376 - 9377, which is incorporated herein by reference in its entirety.

[0062] In another embodiment, the MCPN may be Magnesium Format. The synthesis and properties of Magnesium Format are described in "Phase Transitions and CO2 Adsorption Properties of Polymeric Magnesium Formate", Andrea Rossin et al., Crystal Growth & Design, 2008,8(9), pages 3302 - 3308, which is hereby incorporated here by reference in its entirety.

[0063] In another embodiment, the MCPN can be aluminum terephthalate. The synthesis and properties of aluminum terephthalate are described in "A Rationale for the Large Breathing of Porous Aluminum Terephthalate (MIL-53) Upon Hydration", Loiseau et al., Chemistry - A European Journal, 2004, 10(6): pages 1373 - 1382, which is incorporated herein by reference in its entirety.

[0064] In another embodiment, the MCPN can be Cu3(benzene-1,3,5-tricarboxylate)2. The synthesis and properties of Cu3(benzene-1,3,5-tricarboxylate)2 are described in “Argon Adsorption to Cu3(Benzene-1,3,5-tricarboxylate)2(H2O)3 Metal Organic Framework”, Krungleviciute et al ., Langmuir, 2007. 23(6): pages 3106 - 3109, which is incorporated herein by reference in its entirety.

[0065] In another embodiment, the MCPN can be Fe(1,3,5-benzenetricarboxylate). The synthesis and properties of Fe(1,3,5-benzenetricarboxylate) can be found in “Complexes of Iron(III) Salen and Saloph Schiff Bases with Bridging Dicarboxylic and Tricarboxylic Acids”, Kopel, et al., Transition Metal Chemistry, 1998 23(2): pages 139 - 142, which is incorporated herein by reference in its entirety.

[0066] In another embodiment, the MCPN can be 2-Methylimidazole Zinc Salt. Synthesis and properties of 2-Methylimidazole Zinc salt are described in "A Two-Dimensional Zeolitic Imidazolate Framework with A Cushion-Shaped Cavity for CO2 Adsorption", Chen et al., Chemical Communications, 2013. 49(82): pages 9500 - 9502, which is incorporated herein by reference in its entirety.

[0067] In another embodiment, the MCPN can be Co(2-methylimidazole)2. The synthesis and properties of Co(2-methylimidazole)2 are described in “Hydrothermal Synthesis of Zeolitic Imidazolate Framework-67 (ZIF-67) Nanocrystals”, Qian et al., Materials Letters, 2012. 82(0): pages 220 - 223, which is incorporated herein by reference in its entirety.

[0068] In another embodiment, the MCPN can be Al(OH)fumarate. The synthesis and properties of Al(OH)fumarate are described in "The Structure of the Aluminum Fumarate Metal-Organic Framework A520", Alvarez et al., Angewandte Chemie, 2015, 127(12): pages 3735 - 3739, which is incorporated here by reference in its entirety.

Example 3: Adsorption of 1-MCP on MCPN

[0069]This Example provides specific examples of methods to adsorb 1-MCP onto an MCPN. Adsorption of 1-MCP was performed using either a modified solid method (method A) or a solution-based method (method B), as disclosed herein. The general protocol in both methods included a dual-vessel system, where 1-MCP was generated in the first vessel, also referred to as the generation vessel, and adsorption took place in the second vessel, also referred to as the adsorption vessel. Before adsorption, 50 mg of adsorbent was first dried in a vacuum oven at 100 °C overnight and sealed in the adsorption vessel. About 0.1 atm pressure (100,000 ppm free top concentration) of 1-MCP was generated in the generation vessel and introduced to the adsorption vessel. Adsorption was continued for 20 hours with continuous stirring of the adsorbent.

[0070] During solid-based adsorption with MCPN, 50 mg of dry adsorbent was used for adsorption purposes, and during solution-based adsorption with MCPN, concentration of 1mg/mL of MCPN solution was prepared with distilled water in the generation vessel .

[0071] In another example, the specific MCPN selected was CaSDB. A two jar configuration was used essentially as described above. Briefly, 1-MCP was generated in one jar and adsorption took place in the other jar. 0.05 g of CaSDB was first activated (dried in a vacuum oven at 100 °C overnight) and placed in the adsorption jar where a vacuum was created by a vacuum pump. In the other jar, lithium salt was mixed with water to generate 1-MCP (free top concentration > 0.1 atm or 100,000 ppm). The two jars (1-MCP generation jar and the adsorption jar) were then connected to introduce 1-MCP into the encapsulation jar. Adsorption of 1-MCP continued for 20 hours.

Example 4: Adsorbents (MCPNs) and Encapsulants (Cyclodextrins)

[0072] This Example illustrates some of the MCPNs of the present disclosure and prior art encapsulants (cyclodextrins). Adsorbents (MCPNs) include calcium-4,4'-sulfonyldibenzoic acid (S1), copper-2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine (S2), and zinc -tcbpe (reaction product of tetra-(4-bromo-phenyl)ethylene (tpe-Br) and 4-(methoxycarbonyl)phenylboronic acid) (S3). For comparison, cyclodextrin encapsulants, such as alpha-(S4) and beta-(S5) cyclodextrin, were also used.

Example 5: Encapsulation of 1-MCP in α-Cyclodextrin

[0073] This Example describes the methods used for the encapsulation of 1-MCP in α-cyclodextrin (e.g., for comparison with 1-MCP adsorbed on MCPNs). A jar-in-jar configuration was designed that represented a modified and simplified version of the method described in “Kinetics of Molecular Encapsulation of 1-Methylcyclopropene into α-Cyclodextrin”, Journal of Agricultural and Food Chemistry, 2007, 55(26): pages 11020 - 11026. Briefly, 0.3 g of α-cyclodextrin powder was dissolved in 2 ml of water in a small glass jar (75 ml). Lithium salt was mixed with water in a larger jar (200 mL) to generate 1-MCP (free top concentration > 0.1 atm or 100,000 ppm). The small jar containing the α-cyclodextrin solution was placed in the larger jar, which was then immediately closed and placed on a shaker for 15 hours. The encapsulation complex precipitated out of solution and the precipitate was filtered and dried.

Example 6: Adsorption Levels in Complexes Formed between 1-MCP and MCPNs vs. Encapsulation Levels with Cyclodextrins

[0074] This Example illustrates some of the differences between the MCPNs of the present disclosure and prior art encapsulants (cyclodextrins). Adsorption of 1-MCP using method A and method B was performed in S1 and compared with the encapsulation level in S4. Method B for encapsulation of S4 was modified by making a solution in a pH 4.6 buffer solution to form a concentration of 50 mg S4/mL (method D) (Neoh et al., “Kinetics of Molecular Adsorption of 1- Methylcyclopropene into α-Cyclodextrin”, Journal of Agricultural and Food Chemistry, 2007; 55(26): pages 11020 - 11026). Samples were taken after adsorption (A1)/encapsulation (E4) solution, filtered and allowed to dry to remove excess water. The percentage adsorbed or encapsulated was quantified by taking 55 mg of A1 or E4 and mixing with 25 ml of water in sealed 500 ml glass bottles to release 1-MCP.

[0075] Free top sample was collected and injected in gas chromatography using methods described in Mir, “Harvest Maturity, Storage Temperature and 1-MCP Application Frequency Alter Firmness Retention and Chlorophyll Fluorescence of “Redchief Delicious” Apples”, Journal of American society of horticultural science, 2001, 126(5): 618 - 624). 1-MCP was identified as the peak retention time of 4.8 minutes. Peak area was used to quantify concentration.

[0076] The results of this procedure are shown in Table 2. Adsorption in S1 using either method A or B and encapsulation in S4 using method D in the solution achieved similar adsorption or inclusion level (~2.5%), but inclusion level in S4 using method A was negligible (0.05%). Table 2: Adsorption level or inclusion of 1-MCP in S1 and S4 using method A and method B

[0077] Figures 1A-D illustrate chromatograms of 1-MCP released by solid (Figures 1B and 1C) and solution (Figures 1A and 1D) methods for MCPN adsorption complexes (Figures 1B and 1D) and molecular encapsulation complexes of α-cyclodextrin (Figures 1A and 1C), and show data corresponding to Table 2, according to various embodiments. The chromatograms in Figure 1 show that 1-MCP released from MCPN by both methods A (Figure 1A) and B (Figure 1B) produced peaks of 1-MCP at 4.8 min. The peak areas further illustrate that adsorption on S1 using both methods A and B and encapsulation of S4 using method D in solution (Figure 1D) achieved similar inclusion levels (~2.5%), but the inclusion level at S4 using method A (Figure 1C) was negligible (0.05%). Additionally, the chromatogram in Figure 1D shows some impurity peaks in addition to the 1-MCP peak.

Example 7: Adsorption Levels with Multiple Adsorption Methods on Multiple MCPNs

[0078] This Example showed the adsorption levels of various samples of MCPNs. Adsorption of 1-MCP was performed on Samples of S1, S2 and S3 using method A. Table 3 showed that the adsorption levels on S1 and S3 were 2.5% and 0.3%, respectively, and there was no adsorption on S2. Table 3: Adsorption Level of 1-MCP in S1, S2 and S3 Using Method A

[0079] Figure 2 is a bar graph illustrating levels of inclusion of 1-MCP in various MCPNs (S1, S2 and S3) using a solid adsorption method, and showed data corresponding to Table 3, according to various forms of achievement. Adsorption levels of 1-MCP using method A of adsorption on S1 and S3 were 2.5% and 0.3%, respectively, and there was no adsorption on S2.

Example 8: 1-MCP Release Rate

[0080]This Example illustrates the release rate of 1-MCP from MCPNs and cyclodextrins. 1-MCP release rate was compared between S1 and S4 samples. Adsorption of 1-MCP in S1 sample was performed using both methods A and B. Encapsulation of S4 sample was performed using methods A and D. Method C was used for the release of 1-MCP, where about 25 mg of S1 and S4 were hydrated with 25 ml of water in a 500 ml glass beaker under stirring. Free top samples were taken periodically to quantify released 1-MCP.

[0081] 1-MCP release of S1 method B was instantaneous and complete release was achieved within 5 minutes. Similarly S4 encapsulated by method A released 1-MCP almost instantly. As shown in Table 4, 1-MCP release from S1 method A and S4 method D was in a slow manner, and complete release was achieved within 60 and 40 minutes respectively. Table 4: Release of 1-MCP from S1 (method A) and S4 (method D)

[0082] Figure 3 is a graph illustrating the release of 1-MCP by suspending the encapsulant and the absorbent complexes in water of S1 (method A) and S4 (method D), and showed data corresponding to Table 4, according to with various embodiments. The release of 1-MCP from S1 method A and S4 method D occurred in a slow manner, and complete release was achieved within 60 and 40 minutes, respectively. The release of the S1 adsorbent was slightly slower than that of the S4 encapsulant. S1 release was 27% less at 15 minutes, 8% at 25 minutes and 6% at 40 minutes compared to S4 encapsulant.

Example 9: Release Rate of 1-MCP from S1 and S4 Samples

[0083] This Example illustrates a comparison of 1-MCP release rates from an MCPN and a cyclodextrin. The release rate of 1-MCP was compared between S1 and S4 samples after adsorption and inclusion of 1-MCP. Adsorption of 1-MCP in S1 sample was performed using method A (AS1). Encapsulation of sample S4 was performed using method D (ES4). Method E was used for the release of 1-MCP, where about 25 mg of S1 and S4, containing 1-MCP, was heated to 50 °C. Free top samples were taken periodically to quantify released 1-MCP. Results showed that 1-MCP released completely from AS1 within 90 minutes, however, only about 6% released from ES4 after 360 minutes (6 hours; Table 5).

[0084] Furthermore, the energy required to release 1-MCP from S1 and S4 samples are very different, and yet the means of maintaining 1-MCP in S1 and S4 (eg, adsorption vs. encapsulation) are also very different. many different. A lower amount of energy is sufficient to release 1-MCP from AS1, which may be due to the easy movement of energy through the S1 MCPN structure, while the molecular encapsulation structure of S4 includes a cage structure that makes more levels higher. high energy are needed for both to enter the structure and also to overcome the weak pull forces to release 1-MCP. Table 5: Release of 1-MCP from AS1 and ES4 at 50 °C

[0085] Figure 4 is a graph illustrating the release of 1-MCP from encapsulant and complex absorbents by heating to 50 °C, and showed data corresponding to Table 5, according to various embodiments. As shown in Figure 4, at 50 °C, 1-MCP released completely from AS1 within 90 minutes, however, only about 6% released from ES4 after 360 minutes (6 hours).

Example 10: Recyclability of Adsorbent S1

[0086]This Example demonstrates the recyclability of the S1 adsorbent in release and readsorption of 1-MCP. This recyclability was evaluated by releasing 1-MCP from the adsorbed S1 sample and reusing the adsorbent for subsequent adsorption. Once, 1-MCP was completely released from S1 adsorption, using methods C and E, the resulting adsorbent was separated and used for adsorption again. When method C was used to release 1-MCP, the resulting adsorbent was removed after complete release, cooled and vacuum dried overnight. Then, 25 mg of the dry adsorbent was reused for adsorption of 1-MCP using method A. The S1 sample was able to be recycled, and about 2.5% of adsorption level was obtained with the recycling process.

[0087] When method E was used to release 1-MCP, the resulting adsorbent was removed after complete release by centrifugation process and kept in a vacuum oven overnight to remove water. Then, 25 mg of the dry adsorbent was adsorbed using method A. The S1 sample was able to be recycled, and about 1.01% of adsorption level was obtained with the recycling process.

Example 11: TEM Analysis of MCPN Before and After Adsorption of 1-MCP

[0088] This Example illustrates the structural changes in an MCPN after adsorption of 1-MCP. Tunneling electron microscopy (TEM) analyzes were conducted to visualize the structure before and after adsorption of 1-MCP. Figures 5A and 5B are two digital images showing TEM analyzes of MCPN before and after complex formation with 1-MCP; according to various embodiments.

[0089]As shown in Figure 5A, the control sample surface (before adsorption) is smooth, while, after adsorption (Figure 5B), the surface becomes rough because of the binding of 1-MCP molecules.

Example 12: Bioassay Studies

[0090]This Example demonstrates that 1-MCP released from a MCPN-1-MCP complex exerts the expected biological effects on plant materials. Bioassay studies were performed by releasing 1000 ppb of 1-MCP (volume/volume) from the complex of the invention into the free top of an airtight Pyrex Glass Treatment Chamber 265 containing 50 partially ripened tomatoes (approximately 50% green and 50 % Red). The hermetic lid of the chamber was opened 16 hours after the release of 1-MCP was triggered from an MCPN-1-MCP complex. Release was triggered with water, and after the lid was opened, the chamber's internal atmosphere was allowed to equilibrate to normal ambient air levels of O2 and CO2. A separate batch of 50 tomatoes that were not exposed to 1-MCP served as a control. Both treated and untreated fruits were kept at 22 °C for shelf life evaluation. The control fruit had a shelf life of 7 days, while the fruit treated with 1-MCP released from MCPN-1-MCP complex had a shelf life of 14 days at 22 °C.

Example 13: Testing Commercially Available MCPNs

[0091] This Example illustrates the effectiveness of various commercially available MCPNs in adsorbing 1-MCP. Commercially available MCPNs have been tested alongside laboratory-made MCPNs for their ability to adsorb. MCPNs included calcium 4,4'-sulfonyldibenzoic acid (MCPN-a), magnesium formate (MCPN-b), aluminum terephthalate (MCPN-c), copper benzene-1,3,5-tricarboxylate (MCPN- d), iron 1,3,5-benzenetricarboxylate, (MCPN-e), cobalt formate (MCPN-f), manganese formate (MCPN-g), zinc formate (MCPN-h) and zinc salt of 2-Methylimidazole (MCPN-i). Adsorption of 1-MCP was performed using a two jar configuration substantially as described above. 1-MCP was generated in one jar and adsorption took place in another. Prior to initiation of the adsorption process, about 1g of MCPN was activated in a vacuum oven at 100 °C for at least 8 hours to remove moisture or solvents. MCPN was placed with desiccants in the adsorption jar where a vacuum was created by a vacuum pump.

[0092] In the other jar, lithium salt was mixed with water to generate 1-MCP (free top concentration > 0.1 atm or 100,000 ppm). The two jars (1-MCP generation jar and the adsorption jar) were then connected to introduce 1-MCP into the adsorption jar. Adsorption continued for 20 hours.

[0093] Quantification of adsorbed 1-MCP was performed by mixing the resulting MCPN powder in water in an airtight jar. 1-MCP released into the free top was measured after 1 hour based on the method described by Mir et al., "Harvest Maturity, Storage Temperature and 1-MCP Application Frequency Alter Firmness Retention and Chlorophyll Fluorescence of "Redchief Delicious" Apples" , Journal of the American Society of Horticultural Science, 2001, 126(5): 618 - 624).

[0094] Table 6 demonstrates the adsorption ratio of 1-MCP for different MCPNs ranging from 0.1% to 8.8%. MCPN-b showed the highest adsorption, followed by MCPN-h, MCPN-g and MCPN-f, which were approximately the same level as MCPN-b at 7 between 9% and MCPN-a had the lowest adsorption ratio at 2.3%. Other MCPNs, including MCPN-c, MCPN-d, MCPN-e and MCPN-i had almost no adsorption. Table 6: Adsorption of 1-MCP in MCPNs

Example 14: Evaluation of Adsorption-Desorption Properties of MCPN

[0095]This Example illustrates the adsorption-desorption properties of an MCPN. To evaluate the adsorption-desorption properties of MCPN at 1 atm, isobutene was used as a marker to simulate 1-MCP at 1 atm due to its structural similarity to 1-MCP and molecular weight of Similar. Quantification was conducted using an automatic micro-pore gas analyzer, Autosorb-1 MP (Quantachrome Instruments). Adsorption analysis was conducted under 1 atm of isobutene, and desorption was conducted under 1 atm of air. Alpha cyclodextrin (C-a) and beta cyclodextrin (C-b) were used as controls for comparison purposes.

[0096] Table 7 illustrates that MCPN-b had the highest isobutene uptake of 140 mg/g followed by MCPN-f of 105 mg/g and MCPN-a of 63 mg/g, while there was no uptake for Ca and Cb. The adsorption rate for MCPN-b and MCPN-f was instantaneous which was much faster than MCPN-a, which was almost 10 hours for maximum adsorption. Complete desorption to MCPN-b and MCPN-f occurred within 3 hours, and final uptake after reaching the desorption plateau was low to almost zero. However, desorption to MCPN-a was much slower and was expected to stabilize at a relatively higher uptake level after 10 hours. Table 7: Adsorption-desorption properties of MCPN's for isobutene

Example 15: Stability and Recyclability of MCPN-a in Water

[0097] This Example illustrates the stability and recyclability of MCPN-a in water. X-ray analysis was performed to determine the structural change in MCPN-a before and after hydrolysis. C-a was also analyzed for comparison purposes. Approximately 2 mg of MCPN-a was first soaked separately in 2 ml of water for 1 hour, 5 hours and 20 hours and then dried at 120 °C and filtered to be recycled. X-ray powder diffraction patterns were recorded in an automatic Rigaku D/M-2200T (Ultima+) diffractometer using Cu Kα radiation (À = 1.5406 A). A graphite monochromator was used and generator power settings were 44 kV and 40 mA. Data were collected between 2 theta from 3 to 50 °C at a scan speed of 3.0 °C/min.

[0098] Figures 6A and 6B illustrate X-ray diffraction patterns of MCPN before (Figure 6A) and after (Figure 6B) dissolution in water, according to various embodiments. The X-ray pattern of MCPN-a did not change after water treatment for up to 20 hours, indicating that it is stable and recyclable in water. However, Ca had a dramatic structure change after 1 hour soaking in water. The results indicate another advantage of using MCPN-a as an adsorbent for 1-MCP as compared to C-a as an encapsulant for 1-MCP because of its stability and recyclability in water.

Example 16: Thermal Stability of MCPN

[0099]This Example illustrates the thermal stability of MCPN. Thermogravimetric analysis (TGA) was conducted to determine the temperature that causes structural change in MCPN. MCPN-f and MCPN-b were analyzed and C-a and C-b were used as controls. TGA data were collected on a TA Q5000 Analyzer with a temperature rise rate of 10 °C/min from room temperature to 600 °C under nitrogen gas flow.

[00100] Table 8 illustrates that the decomposition temperature of MCPN-b was 400 °C, which was higher than the decomposition temperature of 275 °C for MCPN-f, which was similar to Ca and Cb. Furthermore, MCPN-b can be recycled as a 1-MCP adsorbent even after heat treatment. Table 8: MCPNs decomposition temperature

Example 17: Stability of Active Ingredient Formulation (AIF) in Capsules and Tablets

[00101] This Example demonstrates the stability of AIF in three types of capsules: MCPN-b/AIF glycerol complex filled capsules (MCPN-G), MCPN-b/AIF filled capsules with liquid formulation (MCPN-LF) and capsules filled with starch and mineral oil (MCPN-SOL). To manufacture MCPN-G, capsules were first filled with MCPN-B/AIF, and approximately 0.6 mL of glycerol was added. To make MCPN-LF, a liquid formulation (mixture of 78% glycerol/9% hydroxypropylcellulose/13% polysorbate) and MCPN-b/AIF was mixed using a vortex mixer for 10 minutes. Approximately 0.5 ml of the mixture was dispensed into each capsule. To make MCPN-SOL, 1.5 g of starch and 0.06 g of MCPN were added to each capsule, and then mineral oil was added to the capsule. The particle size of MCPN in MCPN-LF was less than 0.21 mm. The particle size range of other formulations was approximately 0.21 mm to 1.5 mm.

[00102]The stability of AIF in three tablets was evaluated. MCPN-T1 was manufactured using food grade modified starch as the filler. The composition of an MCPN-T1 was 1.2 g with 0.5% 1-MCP. Excess pressure was used to compress the ingredients into MCPN-T1 tablets. Two materials were tested for MCPN-B1 (1) MCPN-B1a (20% PVOH solution) and (2) MCPN-B1b (50% gelatin solution). Approximately 1 g of coating material was used for MCPN-B1a and MCPN-B1b. After coating, MCPN-B1a and MCPN-B1b were dried for approximately 4 hours. The particle size range of the formulations was approximately 0.21 mm to 1.5 mm. For comparison purposes, a powder formulation without any barrier protection (MCPN-P1) was also tested.

* Determinado pelo limite de detecção do método para AIF (10 ppb)[00103]Table 9 illustrates the retention of AIF in different formulations. The release of MCPN-P1 was instantaneous, and reached saturation within 1 hour after placing it in a closed chamber, and 79% should be the percentage of saturation in 250 mL at a given concentration of AIF. MCPN-T1 improved stability and 87% retention was achieved after 9 days. MCPN-B1 even improved stability. MCPN-B1a and MCPN-B1b improved retention to 94% and 97% after 9 days, respectively. The higher retention of MCPN-B1b was due to the lower permeability of AIF than MCPN-B1a. MCPN-LF and MCPN-SOL had the best retention. MCPN-G achieved greater than 99% retention after 9 days and MCPN-LF and MCPN-SOL had no loss. The slight loss of 1-MCP in MCPN-G on day 4 and onwards was due to glycerol dissolving the gel capsule leading to the loss of 1-MCP. Glycerol itself is impervious to 1-MCP. Table 9: Improved stability of AIF in MCPN

* Determined by method detection limit for AIF (10 ppb)

Example 18: MCPN-LF Uniformity

[00104]This Example illustrates the uniformity of MCPN-LF. After mixing MCPN-B/AIF and dispersing agent (78% glycerol/9% hydroxypropylcellulose/13% polysorbate mixture), five small portions with known amounts of the mixture were dissolved in water in individual sealed jars to release AIF. The particle size of MCPN in MCPN-LF was less than 0.21 mm. Table 10 illustrates that the five portions were uniform with minimal variation. The percentage of AIF in liquid formulation was between 0.194 and 0.198. Table 10: Uniformity of AIF in MCPN-LF

[00105] Although certain embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that a wide variety of alternative and/or equivalent embodiments or implementations calculated to achieve the same purposes may be substituted in place of the embodiments shown and described without departing from scope. Those skilled in the art will easily appreciate that embodiments can be implemented in a very wide variety of ways. This request is intended to cover any adaptations or variations of the embodiments discussed herein. Therefore, it is manifestly intended that embodiments are limited only by the claims and their equivalents.

Claims (15)

1. Adsorption complex CHARACTERIZED by the fact that it comprises 1-methylcyclopropene (1-MCP) and a metal coordination polymer network (MCPN), in which MCPN is a porous material, and 1-MCP is adsorbed on MCPN ; suitably wherein the MCPN has an average pore diameter of 1 to 50 A; where the MCPN comprises a metal knot, and where the metal knot is Mg, Mn, Ca, Cu, Al, Zn, Fe or Co. 2. Adsorption complex according to claim 1, CHARACTERIZED by the fact that MCPN is a magnesium coordination polymer network or a calcium coordination polymer network. 3. Adsorption complex, according to claim 1, CHARACTERIZED by the fact that MCPN is magnesium formate; [Ca(4,4'-sulfonyldibenzoate).H2O]; Cu-TDPAT (also referred to as 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine); Zn2(tcbpe) (also referred to as the reaction product of tetra-(4-bromo-phenyl)ethylene (tpe-Br) and 4-(methoxycarbonyl)phenylboronic acid); [Co3(biphenyldicarboxylate)34,4'bipyridine].4DMF.H2O; [Co(biphenyldicarboxylate)(4,4'bipyridine)].0.5DMF; [Zn2(biphenyldicarboxylate)2(1,2-bipyridylethylene)].2DMF, Mg3(O2C-C10-H6-CO2)3; aluminum terephthalate; Cu3(benzene-1,3,5-tricarboxylate)2; Fe(1,3,5-benzenetricarboxylate); 2-methylimidazole zinc salt; Co(2-methylimidazole)2; or Al(OH)fumarate. 4. Adsorption complex, according to any one of claims 1 to 3, CHARACTERIZED by the fact that MCPN is thermally stable at a temperature of 100 °C to 575 °C; and/or where the MCPN has an accessible pore volume of 1% to 50%; and/or wherein a particle size of the MCPN is from 0.05 mm to 3 mm. 5. Kit to contain 1-MCP CHARACTERIZED in that the kit comprises: an adsorption complex formulation comprising: 1-MCP; and an MCPN, wherein the adsorption complex comprises 0.001 percent by weight to 25 percent by weight of 1-MCP, wherein the MCPN is a porous material, and wherein the 1-MCP is adsorbed onto the MCPN; and a 1-MCP waterproof package, wherein the 1-MCP waterproof package contains the adsorption complex; suitably wherein the 1-MCP waterproof package is a capsule, a flexible bag or a rigid container; or wherein the 1-MCP waterproof package is at least partially soluble in water. 6. Kit, according to claim 5, CHARACTERIZED by the fact that the MCPN has an average pore diameter of 1 to 50 A; and/or wherein the MCPN is a magnesium coordination polymer network or a calcium coordination polymer network; and/or where the MCPN comprises a metal knot, and where the metal knot is Mg, Mn, Ca, Cu, Al, Zn, Fe or Co. 7. Kit, according to claim 5 or 6, CHARACTERIZED by the fact that MCPN is magnesium format; [Ca(4,4'-sulfonyldibenzoate).H2O]; Cu-TDPAT (also referred to as 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine); Zn2(tcbpe) (also referred to as the reaction product of tetra-(4-bromo-phenyl)ethylene (tpe-Br) and 4-(methoxycarbonyl)phenylboronic acid); [Co3(biphenyldicarboxylate)34,4'bipyridine].4DMF.H2O; [Co(biphenyldicarboxylate)(4,4'bipyridine)].0.5DMF; [Zn2(biphenyldicarboxylate)2(1,2-bipyridylethylene)].2DMF, Mg3(O2C-C10-H6-CO2)3; aluminum terephthalate; Cu3(benzene-1,3,5-tricarboxylate)2; Fe(1,3,5-benzenetricarboxylate); 2-methylimidazole zinc salt; Co(2-methylimidazole)2; or Al(OH)fumarate. 8. Kit, according to any one of claims 5 to 7, CHARACTERIZED by the fact that the MCPN is thermally stable at a temperature of 100 °C to 575 °C; and/or where the MCPN has an accessible pore volume of 1% to 50%; and/or wherein 1-MCP is released from the adsorption complex when the MCPN is contacted with at least one aqueous fluid, by heat, or by positive or negative pressure. 9. Method for releasing 1-methylcyclopropene (1-MCP) from an adsorption complex formulation kit, the adsorption complex formulation kit comprising: 1-MCP; an MCPN, wherein the adsorption complex comprises 0.001 percent by weight to 25 percent by weight of 1-MCP, wherein the MCPN is a porous material, and wherein the at least one molecule of 1-MCP is adsorbed onto the MCPN; and a 1-MCP waterproof package, wherein the 1-MCP waterproof package contains the adsorption complex; CHARACTERIZED by the fact that the method comprises contacting the impermeable package of 1-MCP with an aqueous fluid; suitably wherein the 1-MCP waterproof package comprises a water vapor permeable sachet. 10. The method according to claim 9, CHARACTERIZED in that contacting the 1-MCP waterproof package with an aqueous fluid comprises contacting the 1-MCP waterproof package by means of transpiration moisture evolution. 11. Method according to claim 9 or 10, CHARACTERIZED by the fact that the MCPN has an average pore diameter of 50 A or less; and/or wherein the MCPN has a particle diameter of 0.05mm to 3mm; and/or wherein the MCPN is a magnesium coordination polymer network or a calcium coordination polymer network; and/or where the MCPN comprises a metal knot and where the metal knot is Mg, Mn, Ca, Cu, Al, Zn, Fe or Co. 12. Method, according to any one of claims 9 to 11, CHARACTERIZED by the fact that MCPN is magnesium formate; [Ca(4,4'-sulfonyldibenzoate).H2O]; Cu-TDPAT (also referred to as 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine); Zn2(tcbpe) (also referred to as the reaction product of tetra-(4-bromo-phenyl)ethylene (tpe-Br) and 4-(methoxycarbonyl)phenylboronic acid); [Co3(biphenyldicarboxylate)34,4'bipyridine].4DMF.H2O; [Co(biphenyldicarboxylate)(4,4'bipyridine)].0.5DMF; [Zn2(biphenyldicarboxylate)2(1,2-bipyridylethylene)].2DMF, Mg3(O2C-C10-H6-CO2)3; aluminum terephthalate; Cu3(benzene-1,3,5-tricarboxylate)2; Fe(1,3,5-benzenetricarboxylate); 2-methylimidazole zinc salt; Co(2-methylimidazole)2; or Al(OH)fumarate. 13. Method according to any one of claims 9 to 12, CHARACTERIZED by the fact that MCPN is thermally stable at a temperature of 575 °C or less. 14. Method according to any one of claims 9 to 13, CHARACTERIZED by the fact that the MCPN has an accessible pore volume of 50% or less. 15. Method according to any one of claims 9 and 11 to 14, CHARACTERIZED in that contacting the 1-MCP impermeable package with an aqueous fluid comprises contacting the 1-MCP impermeable package by means of transpiration water evolution from a packaged plant or plant parts.

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